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United States Patent G SYNTHETIC DETERGENT COMPOSITIONS Peter T. Vitaleand Muriel Eileen Liftin, Brooklyn, N. Y., assignors toColgate-Palmolive Company, Jersey City, N. L, a corporation of DelawareNo Drawing. Application October 29, 1949, Serial No. 124,511

11 Claims. (Cl. 252-137) The present invention relates to new syntheticdetergent compositions, and, more particularly, to compositions of thetype of sulfated and sulfonated aliphatic acyl-containing detergentshaving improved properties, and to a process for preparing the same.

Various additives have been incorporated in a wide range ofconcentrations to modify the properties of synthetic detergentcompositions in a desired manner. These additives individually mayaffect one or more of the following properties or mechanisms involved inthe action of the detergent composition including foaming, foamstability, dispersion, suspension, interfacial tension, modification ofmicellar structure, etc. In view of the varied nature of many syntheticdetergents, additives in general exhibit a certain degree of specificityof action. Accordingly, there has been a considerable amount ofexperimentation to discover substances which aid the efiiciency of knowndetergent compositions.

It has now been discovered that the simultaneous presence of the higheraliphatic acid amide type compounds and tri-polyphosphates in syntheticdetergent compositions of the aliphatic acyl-containing sulfate andsulfonate type wherein the acyl radical has about 8-22 carbon atoms giveimproved surface-active properties. It is significant moreover that theimprovements in either the detersive power or foaming properties may beof a synergistic order.

The synthetic detergent compositions comprised by the invention containas the active ingredient the surface active synthetic sulfated orsulfonated aliphatic acyl-containing compounds wherein the acyl radicalhas about 8-22 carbonatoms. Within the scope of such definition are the7 higher fatty acid ethanolamide sulfates; the sulphuric acid esters ofpolyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate, tallow diglyceridemonosulfate; the hydroxy sulfonated higher fatty acid esters, e. g.higher fatty acid esters of 2,3 dihydroxy propane sulfonic acid; thehigher fatty acid esters of low molecular weight alkylol sulfonic acids,e. g. oleic acid ester of isethionic acid; and the like. Moreparticularly, it is preferred to use the sulfated and sulfonatedaliphatic carboxylic esters containing at least about 10 carbon atoms,especially those having about twelve to about twenty-six carbon atoms tothe molecule,

which may be derived from fatty oils, mono and di glycerides, partialfatty acid esters and ethers of polyglycols, etc.

These detergents are commonly used in the form of their water solublesalts. Of these, the alkali metal (e. g. sodium, potassium) and ammoniumsalts are preferred though other salts such as the amine, alkylolamine,alkaline earth metal (e. g. calcium, magnesium) salts may be used ifdesired. Their concentration in the detergent compositions of thepresent invention is generally at least about 10, and preferably atleast about 20% by Weight of total solids. Compositions with very highconcentrations of these active ingredients of the order of up to about90% are prepared for specialized uses generally. With 2,733,213 PatentedJan. 31, 1956 built compositions, however, it is preferred to use anactive ingredient content of about 20 to about 50%.

The amides to be used in conjunction with the polyphosphates arepreferably the surface-active higher amide having the formula:

wherein RCO is an aliphatic acyl radical, preferably of a higher fattyacid, having from about 10 to 20, and preferably about 12 to 16 carbonatoms, and X and Y may each be selected from the group consisting ofhydrogen, and alkyl and alkylol radicals of 1 to about 5 carbon atomseach, and preferably about 2 carbon atoms. With the non-alkylolcontaining amides, it is preferred that the acyl radical be about l0-14carbon atoms. With the monoalkylolamides, it is generally preferred thatthe acyl radical be about 10 to 16 carbons, whereas with thedialkylolarnides, acyl radicals of slightly longer chain length of about12 to 20 carbon atoms are preferred generally. Specific examples ofamides which comes Within the scope .of the invention are:palmitylethanolamide, myristylethanolamide, laurylethanolamide,oleylethanolamide, myristamide, lauramide, stearamide, lauricdiethanolamide, and amide type mixtures prepared from mixtures of higherfatty acids derived from various fats, oils, and waxes of animal,vegetable or marine origin.

The polyphosphate additives in the detergent compositions referred toherein are preferably the water soluble inorganic tri-polyphosphates ofthe formula:

M representing an alkali metal (e. g. sodium, potassium) or ammoniumgroup. Y

These additives may be incorporated either together or separately withthe active ingredient at any point during the manufacturing process atwhich subsequent operations will not adversely modify the properties ofthe detergent composition. In general, this addition may be accomplishedby wet-mixing the solid polyphosphates and the amides wtih the activeingredient, or by dry-mixing these materials which are solid undernormal conditions in comminuted form. The best results are not achievedby me chanically intermixing the comminuted solid components. A varietyof procedures, which have proven to be convenient, economical, andproductive of the best results are:

(l) The addition of the solid polyphosphates and molten amides to a hotaqueous slurry of the active ingredient of about 40 to 50% concentrationwith vigorous stirring to form a smooth, uniform and homogeneous paste.

(2) The amides may be dissolved in a suitable solvent, e. g. ethanol,and added to a slurry of the active ingredient, before, during, or afteraddition of the polyphosphates.

(3) A cream emulsion of the polyphosphates and amides in water with aminor proportion of the active ingredient may be prepared andincorporated into the slurry of the active ingredient in the manner setforth above.

Thereafter, these compositions may be made up in the form of solutions,pastes, or as dry or partially hydrated solid products, preferably in afinely divided condition.

The amount of the mixed additives is sufficient to produce a beneficialaction on the detersive or foaming prop erties of the detergentcompositions referred to herein. The amount of amides is minor inproportion to the weight of total solids, and generally varies withinrather definite proportions of the order of about 1 to about 10% andpreferably from about 1 to about 5%. The tri-polyphosphates, however,may be used in any desired proportion. To some extent, the degree ofimprovement appears to be proportional to its content in thecomposition. In general, the greater the percentage oftri-polyphosphate, the better the result where the active ingredient hasbeen maintained constant. For best results, the proportion of phosphateshould be at least 20% by weight, and preferably within the range ofabout 20 to about 50%. An amount of active ingredient of about 20 toabout 50% with about l-% amides, and about 50% polyphosphates producessufficient deterging properties in an aqueous solution for even heavilysoiled laundry; and such composition is economical to prepare andconvenient for use in the home or commercially.

It may be noted that the total washing efiiciency of a detergentcomposition is the result of both the amount of soil removed and theamount redeposited. It has been ascertained that the mixed additives inthe relationship set forth may perform the dual function of bothincreasing the soil removal power and of inhibiting the soilredeposition power generally of the detergent compositions referred toherein. In addition, the mixed additives may effect a synergisticincrease in detergency, particularly in soft water, such that thesealiphatic acyl-containing detergent compositions may possess a highlevel of detersive efficiency in an aqueous solution.

These results are ,evident from a consideration of the following dataand examples which are merely illustrative of the present invention andit will be understood that the invention is not limited thereto.

The effect of these mixed additives may be determined by standard soilremoval and soil redeposition tests. Briefly, these tests involve theaddition of a large number of standard soiled cotton swatches andunsoiled cotton swatches to a detergent solution at 120 F. The system isagitated in a standard manner and the swatches are then rinsed, driedand examined under a Hunter reflectorneter. The increase in reflectanceof the soiled swatches is an indication of the soil removal value andthe decrease in reflectance of the unsoiled cloths is the redepositionvalue. The values in the tablets are expressed in Hunter units X 10 Ahigher value in the soil removal column is an indication of betterwashing power, and lowor values in the soil redeposition column are moredesirable.

The following results are obtained using as standards 0.5%concentrations in distilled water of Formula I which comprises 40% ofthe sodium salts of coconut oil monoglyceride monosulfates and 60%sodium sulfate and Formula II in which sodium tri-polyphosphate has beensubstituted in Formula I for an equivalent quantity of sodium sulfate.Where the presence of varying amounts of amide additives is indicated,these amide additives have been added in percent of total solids in thestandard compositions.

The synergistic improvement in detergency in the relationship set fortheffected by the use of the mixed amide type and tri-polyphosphateadditives is evident from the data. Comparison of the effects ofstandard Formula I and II without the amide additives discloses that thetripolyphoshate has an adverse effect on the soil removal power and amoderate beneficial effect on the amount of soil redeposition. Asindicated with Formula I, the various amide compounds in general havelittle effect on the soil removal or soil redeposition power. Incontradistinction however, the combinations of amide compounds andtri-polyphosphate as exemplified by the results listed under Formula IIhave the unitary effect of markedly improving the soil removal power andinhibiting the soil redeposition power to a significant degree also. Theunexpected and somewhat balanced effects on detersive power achievedwith the mixed additives varies to some degree of course with changes inthe detergent compositions and testing conditions.

From the viewpoint of foaming generally, the novel compositions of thepresent invention may exhibit a high level of foam stability in washingoperations. The fact that the mixed additives may produce foam and sudswhich are more stable, of good creaminess and consistency, do notreadily break down by evaporation, and have in general a longer drainagetime in comparison to the effects of the polyphosphate alone issignificant as these characteristics are desirable generally for adetergent composition. The effect on the foaming properties by the mixedadditives however appears to have some specificity of action. Ingeneral, the amides in conjunction with the polyphosphates appear toexert a more beneficial action on the foaming properties of thedetergent compositions than the alkylolamide compounds in a similarrelationship.

These effects on the foaming characteristics can be studiedquantitatively for a given composition. A pour foam test designed forcomparative study of the relative foam stability of liquids and anappropriate apparatus for carrying out the test is set forth in UnitedStates Patent No. 2,315,983 to Ross and Miles. The foam height inmillimeters of solutions tested in accordance with the Ross and Milespatent is read at various time intervals and is an indication of foamstability.

Table II sets forth the results of comparative pour foam tests at F. inhard water at 0.25% concentrations of a standard detergent composition(A) comprising about 25% sodium salts of coconut oil fatty acidmonoglyceride monosulfates and about 75% sodium sulfate, of a likecomposition (B) in which 50% sodium tri-polyphosphate has beensubstituted for an equivalent quantity of sodium sulfate and of a thirdcomposition (C) which corresponds to composition (B) but in additioncontains 3% myristamide.

It may be noted from the results above that composition (C) containingthe mixed amide and tri-polyphosphate additives has a high level of foamstability in hard water in contradistinction to the marked foambreakdown that occurs using composition (A) which contains neitherdesired additive, and the added adverse effect on the foam produced bythe use of composition (B) containing the tri-polyphosphate additivesolely. In addition, the foam of composition (C) in washing is creamierand of a good degree of consistency. In general, these superior resultsmay be attained in soft water solutions also.

The superior desirable effects of the mixed additives which may beobtained on the foaming properties of these detergent compositions mayalso be evidenced by soil tolerance tests. These tests are essentiallythe pour foam tests modified by the addition of a small amount of a soilto the detergent solution before testing. This procedure represents amore severe test upon the foaming properties of the detergent solution.The results of such tests on compositions A, B (containingtri-polyphosphate), and C (containing the mixed additives) describedsupra are set forth below:

It is evident from the data that composition (C) containing the mixedadditives yields a large volume of foam of a high level of stability incomparison to the effects achieved without the mixed additives.

Though the aliphatic acyl-containing detergents containing the aliphaticamides and polyphosphates may be used as a relatively pure mixture ofthese components, it is common to employ various adjuvant materials insynthetic detergent compositions. These other builders or additives maybe inorganic or organic in structure and may be mixed with the activeingredient in any suitable manner. Such adjuvant materials may includeany of the substances employed by the art in admixture with thesedetergents generally, provided the use of any such materials does notcompletely neutralize or remove the effect of the mixed amide andpolyphosphate additives. It has been found that these added materialsmay vary greatly both in structure and in concentration Withoutimpairing the improved results attained by the compositions of thepresent invention. Thus, such conventional inorganic builders oradditives as the silicates, other alkali metal phosphates (e. g.hexametaphosphate, tetrapyrophosphate), the sulfates, carbonates, etc.,may be employed in these compositions. Organic materials such ascarboxymethylcellulose salts, esters (e. g. ethylene glycolmonostearate, methyl palmitate), and the like may also be used undersuitable conditions.

The following examples of compositions containing the mixed amides andpolyphosphates are also productive of a high level of surface activity.

Example I A detergent composition comprising 30% sodium salts of coconutoil fatty acid monoglyceride monosulfates, 50% sodium tri-polyphosphate,3% sodium silicate, 3% carbonate, 2% palmitylethanolamide and 12% sodiumsulfate is prepared and exhibits good washing properties in an aqueoussolution.

Example 11 An improved detergent composition is prepared containing 25%sodium salts of coconut oil fatty acid monoglyceride monosulfates, 50%sodium tri-polyphosphates, 3% coconut oil fatty acid amides, 3% sodiumsilicate and the remainder essentially sodium sulfate.

Example 111 An improved detergent is prepared by incorporating 3 partsof myristamide in 97 parts of a detergent composition comprising about40% of the condensate of coconut oil fatty acids with isethionic acid asthe active ingredient.

Example IV A detergent of superior properties is prepared byincorporating 3% of myristylethanolamide with a detergent compositioncomprising 40% of the condensate of coconut oil fatty acids with methyltaurine.

Certain general conclusions are apparent from the many tests which havebeen conducted to determine the effect of the mixed additives in theseacyl-containing detergent compositions. The most appropriate mixture ofthe addi tives, their proportion to each other, and their concentrationin each detergent composition may be suitably determined by routinecontrols since the beneficial results vary to some degree of course withchanges in formulation. In each case, the proper washing conditions andthe intended use of the composition (e. g. hard or soft water, generalhome or commercial use, shampoos, ma-

chine washing, etc.) should be taken into consideration in order toderive the maximum beneficial results.

The term consisting essentially of as used in the definition of theingredients present in the composition claimed is intended to excludethe presence of other materials in such amounts as to interferesubstantially with the properties and characteristics possessed by thecomposition set forth but to permit the presence of other materials insuch amounts as not substantially to affect said properties andcharacteristics adversely.

Although the present invention has been described With reference toparticular embodiments and examples it will be apparent to those skilledin the art that variations and modifications of this invention can bemade and that equivalents can be substituted therefor without departingfrom the principles and true spirit of the invention.

Having described the invention, what is desired to be secured by LettersPatent is:

l. A detergent composition comprising about 10 to about 50% ofwater-soluble higher fatty acyl monoglyceride monosulfate detergent salthaving a fatty acyl group of 8 to 22 carbons, in minor proportion tosaid detergent and from about 1 to about 10% of a higher aliphatic amidecompound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms,and X is hydrogen and Y is selected from the group consisting ofhydrogen and alkylol radi-- cals having up to about 5 carbon atoms, andthe balance being primarily water-soluble inorganic builder salts withabout 20% to about 50% tripolyphosphate salt selected RCONHz whereinR-CO is a higher saturated fatty acyl group of about 10 to 14 carbonatoms, and the balance being primarily water-soluble inorganic buildersalts with about 20% to about 50% alkali metal tripolyphosphate, the

above amounts being by weight of total solids of said detergentcomposition.

3. A detergent composition comprising about 10 to about 50% ofwater-soluble higher fatty acyl monoglyceride monosulfate detergent salthaving a fatty acyl group of 8 to 22 carbons, in minor proportion tosaid detergent and from about 1 to about 10% of a higher saturated fattyacyl monoalkylolamide, said fatty acyl group having about 10 to 16carbon atoms and said alkylol group having up to about 5 carbon atoms,and the balance being primarily water-soluble inorganic builder saltswith about 20% to about 50% alkali metal tripolyphosphate, the aboveamounts being by weight of total solids of said detergent composition.

4. A detergent composition comprising about 10 to about 50% ofwater-soluble higher fatty acyl monoglyceride monosulfate detergent salthaving a fatty acyl group of 8 to 22 carbons, in minor proportion tosaid detergent and from about 1 to about 10% of a higher aliphatic amidecompound having the formula:

wherein RCO- is a higher saturated fatty acyl group of about 10 to 14carbon atoms, and the balance being primarily water-soluble inorganicbuilder salts with about 20% to about 50% sodium tripolyphosphate, theabove amounts being by weight of total solids of said detergentcomposition.

5. A detergent composition comprising about 10 to about 50% ofwater-soluble higher fatty acyl monoglyceride monosulfate detergent salthaving a fatty acyl group of 8 to 22 carbons, in minor proportion tosaid detergent and from about 1 to about 10% of a higher saturated fattyacyl monoalkylolamide, said fatty acyl group having about 10 to 16carbon atoms and said alkylol group having up to about carbon atoms, andthe balance being primarily water-soluble inorganic builder salts withabout 20% to about 50% sodium tripolyphosphate, the above amounts beingby weight of total solids of said detergent composition.

6. A detergent composition in accordance with claim 4 wherein said amideis lauramide.

7. A detergent composition in accordance with claim 5 wherein said amideis palmitoylmonoethanolamide.

8. A detergent composition in accordance with claim 5 wherein said amideis lauroylmonoethanolamide.

9. A detergent composition comprising about to about 50% of sodiumhigher fatty acyl monoglyceride monosulfate detergent salt having afatty acyl group of 8 to 22 carbons, in minor proportion to saiddetergent and from about 1 to about 10% of a higher aliphatic: amidecompound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms,and X is hydrogen and Y is selected from the group consisting ofhydrogen and alkylol radicals having up to about 5 carbon atoms, and thebalance being primarily water-soluble inorganic builder salts with about20% to about 50% sodium tripolyphosphate salt, the above amounts beingby weight of total solids of said detergent composition.

10. A detergent composition comprising about 10 to 50% of detergentselected from the group consisting of water-soluble sulfated andsulfonated aliphatic acylcontaining detergent salts wherein the acylradical has about 8 to 22 carbon atoms, in minor proportion to saiddetergent and from about 1 to about 10% of a higher aliphatic amidecompound having the formula:

/X 11-0 O-N wherein RCO is an aliphatic acyl radical of about 10 to 20carbon atoms, and X is hydrogen and Y is selected from the groupconsisting of hydrogen and alkylol radicals having up to about, 5 carbonatoms, and the balance being primarily water-soluble inorganic buildersalts with about 20% to about tripolyphosphate salt selected from thegroup consisting of alkali metal and ammonium tripolyphosphate, theabove amounts being by Weight of total solids of said detergentcomposition.

11. A detergent composition comprising about 10 to 50% of awater-soluble sulfated fatty acyl-containing detergent salt wherein theacyl radical has about 8 to 22 carbon atoms, in minor proportion to saiddetergent and from about 1 to about 10% of a higher aliphatic amidecompound having the formula:

wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms,and X is hydrogen and Y is selected from the group consisting ofhydrogen and a1- kylol radicals having up to about 5 carbon atoms, andthe balance being primarily water-soluble inorganic builder salts withabout 20% to about 50% sodium tripolyphosphate salt, the above amountsbeing by weight of total solids of said detergent composition.

References Cited in the file of this patent UNITED STATES PATENTS2,383,737 Richardson Aug. 28, 1945 2,383,738 Richardson Aug. 28, 19452,383,740 Tucker Aug. 28, 1945 2,396,278 Lind Mar. 12, 1946 2,437,253Henderson Mar. 9, 1948

10. A DETERGENT COMPOSITION COMPRISING ABOUT 10 TO 50% OF DETERGENTSELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE SULFATED ANDSULFONATED ALIPHATIC ACYLCONTAINING DETERGENT SALTS WHEREIN THE ACYLRADICAL HAS ABOUT 8 TO 22 CARBON ATOMS, IN MINOR PROPORTION TO SAIDDETERGENT AND FROM ABOUT 1 TO ABOUT 10% OF A HIGHER ALIPHATIC AMIDECOMPOUND HAVING THE FORMULA: